Carotene composition and process of preparing solutions of carotene



Patented Aug. 2, 949

CAROTENE COMPOSITION AND PROCESS OF PREPARING SOLUTIONS OF CAROTENE Miner L. Hartmann, Beverly Hills, and Harold M. Barnett, Long Beach, Calif.; said Hartmann assignor to said Barnett No Drawing. Application November 4, 1941, Serial No. 784,074

' 15 Claims.

' 'This invention relates to a carotene composition and to a process for preparing solutions irom'crystalline carotene.

One object o! the invention is to provide a method for making solutions from the crystalline form of carotene in edible solvents and oil containlng food products in which the carotene is only slightly soluble. Another object is to provide a method for making a solution from crystalline carotene without loss of vitamin activity of the carotene due to molecular rearrangement caused by heating. Another object is to provide a new'composltion of easily soluble crystalline carotene which does not oxidize rapidly in storage. Another oblect is to provide a suspension of crystalline carotene particles in which the crystals do not grow. A further object is to provide a readily soluble form of crystalline carotene of highly concentrated vitamin activity which will dissolve readily without warming. j These and other objects are attained by the invention which will be understoodfrom the following description.

Carotene, particularly beta-carotene, is an industrially important yellow coloring material as well as a pro-vitamin which is converted in the animal metabolic processes to vitamin A. Carotene is extracted and concentrated from vegetable sources such as carrots, in which it occurs in amounts of about two ounces per ton of carrots, and consequently it has a high unit cost of production. The crystalline form of carotene is highly preferred because of its freedom from noxious flavors and odors which are present in the concentrated extracts of carotene with other plant pigments which are sometimes supplied to the food industry. Carotene is only slightly soluble in oils, the solubility amounting to not more than about three-tenths percent at ordinary room temperature. The solubility in oil increases when the oil is heated but upon heating, a part of the carotene is chemically transformed irreversibly to an inactive carotene or to some unidentified inactive decomposition or rearrangement product, the amount of degradation increasing rapidly as the temperature is increased. In one case, the loss of active carotene was 12 percent at 115 0.; 20 percent at 130 C.; 30 percent at 150 C.; and becoming almost completelytransformed at the melting point, about 170 C.

The problem of making oil solutions, particularly concentrated solutions, from crystalline carotene has remained unsolved from a practical point of view. The mo'stused present method of is added to such foods.

from the point of view of its vitamin and coloring potency. The preparation of solutions of crystalline carotene under-the higher temperatures which cause thislrearrangement', also results in an oiT-flavor which is detectable in the more delicately-flavored foods when this carotene Since crystalline carotene is necessarily a high costmaterial, this inherent loss of potency in preparing the material in an acceptable form for shipment and distribution adds to its ultimate cost to the consumer, and represents an unreclaimable economic loss. The heavy cost of shipping large volumes of oil containing the maximum amount of carotene which can be dissolved at ordinary temperatures is also overcome by our invention. It is desirable to have the carotene in as concentrated form as possible for shipment to food processing plants and the like where it is normally incorporated with other food materials, usually dissolved in oilcontaining foods such as, for example, margarine, butter, salad dressings, milk and the like. A readily soluble concentrated form is desirable in pharmaceutical preparations, vitamin capsules, etc. It has been found that a paste consisting of very finely divided microscopic particles of carotene suspended in a. liquid which is edible, miscible with oil or oily products, and which is also an oxidation protective liquid, may be prepared and used to overcome the above enumerated difficulties. which has as high as50 percent by weight of carotene in cottonseed oil, equivalent to 376 mil lion vitamin A units per pound. The highest concentration of pure carotene in cottonseed oil or equivalent oils commercially available is about four million units. The new paste composition may be employed to produce the dilute solutions of carotene employed in the' food industries. Crystalline carotene is disintegrated to microscopically small particles, for example, by means of a ball mill using a small amount of the selected Such a paste product may be made I ide gas.

ture is not deleteriously increased by the grinding action. It is also important to displace the air in the grinding equipment by an inert gas medium such as pure nitrogen or pure carbon diox- The time of grinding is determined by the size and proportion of the balls and other factors which are common to the operation of comminution by means of ball mills. The material is pulverized until substantially all particles have mean diameters of less than ten microns and many particles are of the order of one or two microns in diameter. The proportion of liquid to carotene is preferably that which at operating temperatures forms a stiff paste but one which fiows enough in the ball mill to give effective commi'nution. It has been found, for example, that 100 grams of carotene may be ground in a ball mill with 300 grams of cottonseed oil.

until by microscopic test no particles are larger than ten microns measured as mean diameters. The product is a pastewhich will barely flow and which has a specific gravity of 0.9. Such a product has been found to remain in uniform suspension for an indefinitely long period of time, and microscopic examination over a period of twelve months disclosed no segregation of the larger particles toward the bottom of the container.

The paste composition of crystalline carotene and a liquid may also be prepared by passage of the mixture through a so-called colloid mill, par= ticularly one of the closely spaced plate type, although the ball-mill process has given a more uniform product.

The preferred liquid medium is a vegetable oil such as cottonseed oil. However, other oils in-= eluding mineral oils, vegetable oils, and animal oils, may be used as well as non-oily liquid media, such as for example, alcohols, glycerine, syrup, lecithin, liquid egg albumin, water, and the like. It is not necessary to use a liquid medium in which the carotene dissolves and it is, in some cases, advantageous to use a liquid media in which carotene is substantially insoluble since, with such media, there is no danger of recrystalization and growth of the finest particles of carotene to form larger and slower dissolving particles in the paste. For use as a concentrated form of carotene in making dilute solutions with a minimum dissolving time, it is desirable to have every particle of carotene as fine as is practicable, and the use of a non-dissolving liquid such as water or lecithin media prevents any growth.

A medium may be selected which at room or refrigerated temperatures is solid, but which be-- comes liquid at only slightly elevated operating temperatures, such as butter oil, paraflin, or lard. These materials have the advantage of providing a solid concentrated form of carotene which becomes readily dispersible and soluble in liquid oils and food products at slightly elevated temperatures sufiicient to melt such media, and also prevent any coalescing of the fine carotene particles.

The process of making a dilute solution of carotene in an edible solvent or to disperse the carotene in an oil-containing food product consists in adding the desired amount of the above highly concentrated form of carotene paste to the edible solvent or food product and then distributing the paste throughout the mixture while maintaining the temperature of the mixture at a suflicient low temperature so that none or only a little the carotene is transformed to the inactive varl ties noted above. The liquid media of the partic1 lar paste product being used may be selected that it is easily miscible with the edible solve: (usually oil) or other food product. It'has be: found that the carotene is quickly dissolved fro the distributed paste, since the particles are an ultra fine form in which they existed in tl paste and therefore are quickly dissolved.

The advantages of the concentrated pas form of carotene of this invention have be: pointed out. The liquid media used in makir the paste provides the protective coating for tl microscopically fine carotene which prevents i oxidation which would otherwise be quite rap: unless completely protected from air. The cor centrated form and easy solubility of the pas composition of carotene makes its packagin shipping, and proportioning both convenient an economical, either in liquid paste or as a SOIidifli paste. The invention provides a practical mear for distributing crystalline carotene in food In: terials, thus taking advantage of the outstandlr characteristic of pure crystalline carotene whic is freedom from undesired odors and flavors.

We claim:

1. A composition of matter containing as e: sential ingredients finely divided particles crystalline carotene in a stable suspension in a edible liquid, said particles having mean dian eters of less than ten microns.

2. A composition of matter containing as e: sential ingredients finely divided particles i crystaiiine carotene in a stable suspension in a edible oil miscible liquid, said particles havir mean diameters of less than ten microns.

3. A composition of matter containing as es sential ingredients finely divided particles crystalline carotene in a stable suspension 1 liquid medium in which said carotene is substar tially insoluble. said particles having mean d ameters of less than ten microns.

4. A composition of matter containing as e: sential ingredients finely divided particles e crystalline carotene in a stable suspension in an edible oil, said particles having mean diametei of less than ten microns.

5. A composition of matter containing as e: sential ingredients finely divided particles 4 crystalline carotene in a stable suspension in a oily medium which is liquid at the temperatui of forming said suspension but becomes solidifie by cooling after said suspension is formed, sai particles having mean diameters of less than to microns.

6. A composition of matter containing as e: sential ingredients finely divided particles 4 crystalline carotene in a stable suspension 1 butter oil, said particles having mean diametei of less than ten microns.

7. A composition of matter containing as esser tial ingredients finely divided particles of crystal line carotene in a stable suspension in paraflb said particles having mean diameters of less tha ten microns.

8. A composition of matter containing as esser tial ingredients finely divided particles of cry: talline carotene in a stable suspension in lar said particles having mean diameters 01 less the ten microns.

9. The method of preparing a solid, oil-solubl carotene composition comprising the steps forming a paste suspension of comminuted cry:

talline carotene substantially all of the particles of which have mean diameters of less than ten microns inan oil which is liquid at the temperature of forming said suspension, and then, cooling said liquid suspension until said paste is a solid.

10. The method of preparing a solid, oil-soluble carotene composition comprising the steps of forming a paste suspension of comminuted crys-' talline carotene substantially all of the particles of which have mean diameters of less than ten microns in lard, and then cooling said liquid suspension until said paste is a solid.

12. The process of making a solution'of crystalline carotene in an edible solvent comprising forming an edible paste of a liquid and fine particles of crystalline carotene substantially all of which have mean diameters of 7 less than ten microns, and then distributing said paste in said edible solvent.

13. The process of making a solution of crystalline carotene in an edible oil comprising forming a paste of an edible oil and fine particles of crys talline carotene substantially all of which have mean diameters of less than ten microns. and then distributing said paste in said edible oil while maintaining the materials at a temperature below about 115 0.

14. The process of making a solution of crystalline carotene in an oil-containing food material comprising forming a paste of an edible liquid and fine particlesof crystalline carotene substantially all of which have mean diameters of less than ten microns, and then distributing said paste in said food material while maintaining the materials at a temperature below about 115 centigrade.

15. The process of making a solution of crystalline carotene in an oil-containing food material comprising forming a paste of a liquid edible oil and fine particles of crystalline carotene substantially all of whlchhave mean diameters b1 less than ten microns, and then distributing said paste in said food material while maintaining the materials at a temperature below the inactivation temperature of the carotene.

an mations man The following references are of record in thz file of this patent:

UNITED STATES PA 01 '1 Li 

